The Daphniphyllum Alkaloids: Total Synthesis of (−)-Calyciphylline N

Presented here is a full account on the development of a strategy culminating in the first total synthesis of the architecturally complex daphni­phyllum alkaloid, (−)-calyci­phylline N. Highlights of the approach include a highly diastereo­selective, intra­molecular Diels–Alder reaction of a silicon-tethered acrylate; an efficient Stille carbonyl­ation of a sterically encumbered vinyl triflate; a one-pot Nazarov cyclization/​proto-desilyl­ation sequence; and the chemo­selective hydrogenation of a fully substituted diene ester